Ring opening cross metathesis of vinyl terminated polymers and their functionalized derivatives for fouling mitigation in hydrocarbon refining processes

ABSTRACT

A compound useful for reducing fouling in a hydrocarbon refining process is provided. A method for preparing the compound includes functionalizing a polymer having a vinyl chain end to obtain a terminal group having one or more anhydride units, and reacting the anhydride units with a polyamine. Methods of using the compound and compositions thereof are also provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.13/804,907 filed on Mar. 14, 2013 and recently allowed, which itselfrelates to International Application PCT/US2012/059191, filed on Oct. 8,2012, the disclosure of which is incorporated by reference in itsentirety herein.

This application is related co-pending U.S. application, filed on theeven date herewith, and identified by Ser. No. 15/131,461 also entitled“Ring Opening Cross Metathesis of Vinyl Terminated Polymers and TheirFunctionalized Derivatives for Fouling Mitigation in HydrocarbonRefining Processes” and is hereby incorporated by reference herein inits entirety.

This application is also related to the following U.S. PatentApplications: U.S. Ser. No. 13/826,512 filed on Mar. 14, 2013; U.S. Ser.No. 13/826,059 filed on Mar. 14, 2013 and granted (U.S. Pat. No.9,212,326) on Dec. 15, 2015; U.S. Ser. No. 13/804,727 filed on Mar. 14,2013 and allowed Aug. 26, 2015; U.S. Ser. No. 13/804,507 filed on Mar.14, 2013 and granted (U.S. Pat. No. 9,085,737) on Jul. 21, 2015; U.S.Ser. No. 14/711,144 filed on May 13, 2015; U.S. Ser. No. 14/870,665filed on Sep. 30, 2015; U.S. Ser. No. 14/870,839 filed on Sep. 30, 2015;U.S. Ser. No. 14/935,978 filed on Nov. 9, 2015; U.S. Ser. No. 14/950,316filed on Nov. 24, 2015; and U.S. Ser. No. 14/950,460 filed on Nov. 24,2015, each of which is hereby incorporated in its entirety by referenceherein.

TECHNICAL FIELD

The disclosed subject matter relates to additives to reduce fouling ofcrude hydrocarbon refinery components, and methods and systems using thesame.

BACKGROUND

Petroleum refineries incur additional energy costs, perhaps billions peryear, due to fouling and the resulting attendant inefficiencies causedby the fouling. More particularly, thermal processing of crude oils,blends and fractions in heat transfer equipment, such as heatexchangers, is hampered by the deposition of insoluble asphaltenes andother contaminants (i.e., particulates, salts, etc.) that may be foundin crude oils. Further, the asphaltenes and other organics are known tothermally degrade to coke when exposed to high heater tube surfacetemperatures.

Fouling in heat exchangers receiving petroleum-type process streams canresult from a number of mechanisms including chemical reactions,corrosion, deposit of existing insoluble impurities in the stream, anddeposit of materials rendered insoluble by the temperature difference(ΔT) between the process stream and the heat exchanger wall. Forexample, naturally-occurring asphaltenes can precipitate from the crudeoil process stream, thermally degrade to form a coke and adhere to thehot surfaces. Further, the high ΔT found in heat transfer operationsresult in high surface or skin temperatures when the process stream isintroduced to the heater tube surfaces, which contributes to theprecipitation of insoluble particulates. Another common cause of foulingis attributable to the presence of salts, particulates and impurities(e.g., inorganic contaminants) found in the crude oil stream. Forexample, iron oxide/sulfide, calcium carbonate, silica, sodium chlorideand calcium chloride have all been found to attach directly to thesurface of a fouled heater rod and throughout the coke deposit. Thesesolids promote and/or enable additional fouling of crude oils.

The buildup of insoluble deposits in heat transfer equipment creates anunwanted insulating effect and reduces the heat transfer efficiency.Fouling also reduces the cross-sectional area of process equipment,which decreases flow rates and desired pressure differentials to provideless than optimal operation. To overcome these disadvantages, heattransfer equipment are ordinarily taken offline and cleaned mechanicallyor chemically cleaned, resulting in lost production time.

There is a need to reduce precipitation/adherence of particulates andasphaltenes from the heated surface to prevent fouling, particularlybefore the asphaltenes are thermally degraded or coked. Such reductionwill improve the performance of the heat transfer equipment, decrease oreliminate scheduled outages for fouling mitigation efforts, and reduceenergy costs associated with the processing activity.

Antifoulant additives have been described in a number of commonly-ownedapplications, including U.S. Patent Application Publication Nos.20110147275 and 20100170829, the disclosure of each of which isincorporated herein by reference in its entirety. However, there remainsa need for alternative antifoulant additives capable of reducingprecipitation and/or adherence of particulates and asphaltenes.

SUMMARY

In accordance with one aspect of the disclosed subject matter, acompound is provided. The compound being represented by

wherein R₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup;

y is an integer between 1 to 20 inclusive;

m is an integer between 0 and 10 inclusive;

a and b are C—C bonds in cis-configuration with respect to each otherand in either cis- or trans-configuration with respect to bond c;

R₂ and R₃ are each independently a C₁-C₄ branched or straight chainedalkylene group;

R₃₁ is hydrogen or —R₈-R₉, wherein either (a) R₈ is C₁-C₄ branched orstraight chained alkylene group, and R₉ is

wherein R₉₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup, the asterisk (*) indicates a connecting point with R₈, d and eare C—C bonds in cis-configuration with respect to each other and ineither cis- or trans-configuration with respect to bond f, and z is aninteger between 1 to 20 inclusive; or (b) R₈ and R₉ together are a C₁-C₄branched or straight chained alkyl group optionally substituted with oneor more amine groups; and wherein the —N(R₃₁)—R₃— repeat unit isoptionally interrupted in one or more places by a nitrogen-containingheterocyclic cycloalkyl group; and

wherein R₄ and R₅ are each independently selected from (a) hydrogen, (b)—R₆-R₇, wherein R₆ is C₁-C₄ branched or straight chained alkylene group,and R₇ is

wherein R₇₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup, the asterisk (*) indicates a connecting point with R₆, g and hare C—C bonds in cis-configuration with respect to each other and ineither cis- or trans-configuration with respect to bond j, and q is aninteger between 1 to 20 inclusive; or (c) a bond connected to R₃₁ in them-th —N(R₃₁)—R₃— repeat unit.

According to another aspect of the disclosed subject matter, a methodfor preparing a compound is provided. The method includes:

(a) converting a polymer base unit R₁₁, which is a branched orstraight-chained C₁₀-C₈₀₀ alkyl or alkenyl group having a vinyl terminalgroup, to a polymer having polyanhydride terminal group represented by:

wherein y is an integer between 1 and 20 inclusive, a and b are C—Cbonds in cis-configuration with respect to each other and in either cis-or trans-configuration with respect to bond c; and

(b) reacting the polymer obtained in (a) with a polyamine represented by

wherein R₁₂ is hydrogen or a C₁-C₄ branched or straight chained alkyloptionally substituted with one or more amine groups, R₁₃ is a C₁-C₄branched or straight chained alkylene group, and x is an integer between1 and 10, and further wherein the —N(R₁₂)—R₁₃— unit is optionallyinterrupted in one or more places by a nitrogen-containing heterocycliccycloalkyl group, and wherein when the x-th —N(R₁₂)—R₁₃— unit along withthe terminal nitrogen atom forms a heterocyclic cycloalkyl group, theterminal —NH₂ is replaced by a —NH— group for valency.

According to a further aspect of the disclosed subject matter, acompound prepared by the above method is provided.

According to yet another aspect of the disclosed subject matter, amethod for reducing fouling in a hydrocarbon refining process isprovided. The method includes providing a crude hydrocarbon for arefining process; and adding an additive to the crude hydrocarbon, theadditive being represented by:

wherein R₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup;

y is an integer between 1 to 20 inclusive;

m is an integer between 0 and 10 inclusive;

a and b are C—C bonds in cis-configuration with respect to each otherand in either cis- or trans-configuration with respect to bond c;

R₂ and R₃ are each independently a C₁-C₄ branched or straight chainedalkylene group;

R₃₁ is hydrogen or —R₈-R₉, wherein either (a) R₈ is C₁-C₄ branched orstraight chained alkylene group, and R₉ is

wherein R₉₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup, the asterisk (*) indicates a connecting point with R₈, d and eare C—C bonds in cis-configuration with respect to each other and ineither cis- or trans-configuration with respect to bond f, and z is aninteger between 1 to 20 inclusive; or (b) R₈ and R₉ together are a C₁-C₄branched or straight chained alkyl group optionally substituted with oneor more amine groups; and wherein the —N(R₃₁)—R₃— repeat unit isoptionally interrupted in one or more places by a nitrogen-containingheterocyclic cycloalkyl group; and

-   -   wherein R₄ and R₅ are each independently selected from (a)        hydrogen, (b) —R₆-R₇, wherein R₆ is C₁-C₄ branched or straight        chained alkylene group, and R₇ is

wherein R₇₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup, the asterisk (*) indicates a connecting point with R₆, g and hare C—C bonds in cis-configuration with respect to each other and ineither cis- or trans-configuration with respect to bond j, and q is aninteger between 1 to 20 inclusive; or (c) a bond connected to R₃₁ in them-th —N(R₃₁)—R₃— repeat unit.

In addition, the disclosed subject matter provides the additives asdescribed in the above methods, antifouling compositions comprising suchadditives, and systems for refining hydrocarbons containing suchadditives and compositions.

BRIEF DESCRIPTION OF THE DRAWINGS

The disclosed subject matter will now be described in conjunction withthe accompanying drawings in which:

FIG. 1 is a representation of an oil refinery crude pre-heat train,annotated to show non-limiting injection points for the additives of thedisclosed subject matter.

FIG. 2 is a schematic of the Alcor Hot Liquid Process Simulator (HLPS)employed in Example 2 of this application.

FIG. 3 is a graph demonstrating the effects of fouling of a controlcrude oil blend sample and a crude oil blend sample treated with 25 wppmof an additive according to the disclosed subject matter, as measured bythe Alcor HLPS apparatus depicted in FIG. 2.

DETAILED DESCRIPTION Definitions

The following definitions are provided for purpose of illustration andnot limitation.

As used herein, the term “fouling” generally refers to the accumulationof unwanted materials on the surfaces of processing equipment or thelike, particularly processing equipment in a hydrocarbon refiningprocess.

As used herein, the term “particulate-induced fouling” generally refersto fouling caused primarily by the presence of variable amounts oforganic or inorganic particulates. Organic particulates (such asprecipitated asphaltenes and coke particles) include, but are notlimited to, insoluble matter precipitated out of solution upon changesin process conditions (e.g., temperature, pressure, or concentrationchanges) or a change in the composition of the feed stream (e.g.,changes due to the occurrence of a chemical reaction). Inorganicparticulates include, but are not limited to, silica, iron oxide, ironsulfide, alkaline earth metal oxide, sodium chloride, calcium chlorideand other inorganic salts. One major source of these particulatesresults from incomplete solids removal during desalting and/or otherparticulate removing processes. Solids promote the fouling of crude oilsand blends due to physical effects by modifying the surface area of heattransfer equipment, allowing for longer holdup times at walltemperatures and causing coke formation from asphaltenes and/or crudeoil(s).

As used herein, the term “alkyl” refers to a monovalent hydrocarbongroup containing no double or triple bonds and arranged in a branched orstraight chain.

As used herein, the term “alkylene” refers to a divalent hydrocarbongroup containing no double or triple bonds and arranged in a branched orstraight chain.

As used herein, the term “alkenyl” refers to a monovalent hydrocarbongroup containing one or more double bonds and arranged in a branched orstraight chain.

As used herein, a “hydrocarbyl” group refers to any univalent radicalthat is derived from a hydrocarbon, including univalent alkyl, aryl andcycloalkyl groups.

As used herein, the term “crude hydrocarbon refinery component”generally refers to an apparatus or instrumentality of a process torefine crude hydrocarbons, such as an oil refinery process, which is, orcan be, susceptible to fouling. Crude hydrocarbon refinery componentsinclude, but are not limited to, heat transfer components such as a heatexchanger, a furnace, a crude preheater, a coker preheater, or any otherheaters, a FCC slurry bottom, a debutanizer exchanger/tower, otherfeed/effluent exchangers and furnace air preheaters in refineryfacilities, flare compressor components in refinery facilities and steamcracker/reformer tubes in petrochemical facilities. Crude hydrocarbonrefinery components can also include other instrumentalities in whichheat transfer can take place, such as a fractionation or distillationcolumn, a scrubber, a reactor, a liquid-jacketed tank, a pipestill, acoker and a visbreaker. It is understood that “crude hydrocarbonrefinery components,” as used herein, encompasses tubes, piping, bafflesand other process transport mechanisms that are internal to, at leastpartially constitute, and/or are in direct fluid communication with, anyone of the above-mentioned crude hydrocarbon refinery components.

As used herein, a reduction (or “reducing”) particulate-induced foulingis generally achieved when the ability of particulates to adhere toheated equipment surfaces is reduced, thereby mitigating their impact onthe promotion of the fouling of crude oil(s), blends, and other refineryprocess streams.

As used herein, reference to a group being a particular polymer (e.g.,polypropylene or poly(ethylene-co-propylene) encompasses polymers thatcontain primarily the respective monomer along with negligible amountsof other substitutions and/or interruptions along polymer chain. Inother words, reference to a group being a polypropylene group does notrequire that the group consist of 100% propylene monomers without anylinking groups, substitutions, impurities or other substituents (e.g.,alkylene or alkenylene substituents). Such impurities or othersubstituents can be present in relatively minor amounts so long as theydo not affect the industrial performance of the additive, as compared tothe same additive containing the respective polymer substituent with100% purity.

For the purposes of the present application, when a polymer is referredto as comprising an olefin, the olefin present in the polymer is thepolymerized form of the olefin.

As used herein, a copolymer is a polymer comprising at least twodifferent monomer units (such as propylene and ethylene). A homo-polymeris a polymer comprising units of the same monomer (such as propylene). Apropylene polymer is a polymer having at least 50 mole % of propylene.

The term “vinyl termination”, also referred to as “allyl chain end(s)”or “vinyl content” is defined to be a polymer having at least oneterminus represented by:

where the “••••” represents the polymer chain.

In a preferred embodiment the allyl chain end is represented by:

The amount of allyl chain ends (also called % vinyl termination) isdetermined using ¹H NMR at 120° C. using deuterated tetrachloroethane asthe solvent on a 500 MHz machine and in selected cases confirmed by ¹³CNMR. Resconi has reported proton and carbon assignments (neatperdeuterated tetrachloroethane used for proton spectra while a 50:50mixture of normal and perdeuterated tetrachloroethane was used forcarbon spectra; all spectra were recorded at 100° C. on a Bruker AM 300spectrometer operating at 300 MHz for proton and 75.43 MHz for carbon)for vinyl terminated propylene polymers in J American Chemical Soc 1141992, 1025-1032, hereby incorporated by reference in its entirety, thatare useful herein.

“Isobutyl chain end” is defined to be a polymer having at least oneterminus represented by the formula:

where M represents the polymer chain. In an example embodiment, theisobutyl chain end is represented by one of the following formulae:

where M represents the polymer chain.

The “isobutyl chain end to allylic vinyl group ratio” is defined to bethe ratio of the percentage of isobutyl chain ends to the percentage ofallylic vinyl groups.

As used herein, the term “polymer” refers to a chain of monomers havinga Mn of 100 g/mol and above.

Reference will now be made to various aspects of the disclosed subjectmatter in view of the definitions above.

In one aspect, the additives of the disclosed subject matter caninteract with the materials in crude oils in a refinery or the like thatare prone to cause fouling, e.g., particulate impurities/contaminantsand asphaltenes. The interaction can be physical or chemical such asabsorption, association, or chemical bonding. The fouling materials canbe rendered more soluble in the crude oils as a result of interactionwith the antifouling additives, therefore the fouling on the exchangermetal surfaces can be reduced or eliminated.

In accordance with one aspect of the disclosed subject matter, acompound (additive) is provided, represented by

wherein R₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup;

y is an integer between 1 to 20 inclusive;

m is an integer between 0 and 10 inclusive;

a and b are C—C bonds in cis-configuration with respect to each otherand in either cis- or trans-configuration with respect to bond c;

R₂ and R₃ are each independently a C₁-C₄ branched or straight chainedalkylene group;

R₃₁ is hydrogen or —R₈-R₉, wherein either (a) R₈ is C₁-C₄ branched orstraight chained alkylene group, and R₉ is

wherein R₉₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup, the asterisk (*) indicates a connecting point with R₈, d and eare C—C bonds in cis-configuration with respect to each other and ineither cis- or trans-configuration with respect to bond f, and z is aninteger between 1 to 20 inclusive; or (b) R₈ and R₉ together are a C₁-C₄branched or straight chained alkyl group optionally substituted with oneor more amine groups; and wherein the —N(R₃₁)—R₃— repeat unit isoptionally interrupted in one or more places by a nitrogen-containingheterocyclic cycloalkyl group; and

-   -   wherein R₄ and R₅ are each independently selected from (a)        hydrogen, (b) —R₆-R₇, wherein R₆ is C₁-C₄ branched or straight        chained alkylene group, and R₇ is

wherein R₇₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup, the asterisk (*) indicates a connecting point with R₆, g and hare C—C bonds in cis-configuration with respect to each other and ineither cis- or trans-configuration with respect to bond j, and q is aninteger between 1 to 20 inclusive; or (c) a bond connected to R₃₁ in them-th —N(R₃₁)—R₃— repeat unit. In certain embodiments of the compound, ycan be an integer between 1 and 10 inclusive, or between 1 and 5inclusive.

In certain embodiments, at least one of R₁, R₇₁, and R₉₁ of the compoundof Formula I shown above comprises polypropylene (PP), which can beatactic polypropylene or isotactic polypropylene. The polypropylene canbe amorphous, and can include isotactic or syndiotactic crystallizableunits. In some embodiments, the polypropylene includes meso diadsconstituting from about 30% to about 99.5% of the total diads of thepolypropylene. In alternative embodiments, at least one of R₁, R₇₁, andR₉₁ of the compound of Formula I comprises polyethylene (PE).

In a further embodiment, at least one of R₁, R₇₁, and R₉₁ of theadditive of Formula I comprises poly(ethylene-co-propylene) (EP). Themole percentage of the ethylene units and propylene units in thepoly(ethylene-co-propylene) can vary. For example, in some embodiments,the poly(ethylene-co-propylene) can contain about 1 to about 90 mole %of ethylene units and about 99 to about 10 mole % propylene units. Inother embodiments, the poly(ethylene-co-propylene) can contain about 10to about 90 mole % of ethylene units and about 90 to about 10 mole %propylene units. In certain embodiments, the poly(ethylene-co-propylene)contains about 20 to about 50 mole % of ethylene units.

In some embodiments of the above method, at least one of R₁, R₇₁, andR₉₁ of the additive of Formula I has a number-averaged molecular weightof from about 300 to about 30,000 g/mol (assuming one olefinunsaturation per chain, as measured by ¹H NMR). Alternatively, at leastone of R₁, R₇₁, and R₉₁ of the additive of Formula I has anumber-averaged molecular weight of from about 500 to 5,000 g/mol. Inone embodiment, the PP or EP included in the R₁, R₇₁, or R₉₁ of theadditive Formula I, individually, has a molecular weight (Mn) from about300 to about 30,000 g/mol, or from about 500 to about 5000 g/mol. In oneembodiment, the PP or EP groups have a molecular weight, individually,ranging from about 500 to about 2500 g/mol, or a molecular of from about500 to about 650 g/mol, or a molecular weight of from about 800 to about1000 g/mol, or a molecular weight of from about 2000 to about 2500g/mol.

In other embodiments of the compound, at least one of R₁, R₇₁, and R₉₁comprises poly(higher alpha-olefin) or poly(propylene-co-higheralpha-olefin), the higher alpha-olefin including two or more carbonatoms on each side chain. For example, suitable higher alpha-olefins caninclude, but are not limited to, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene and the like.

In certain embodiments of the above compound, the nitrogen content inthe compound of Formula I is about 1 wt % to about 10 wt % based on thetotal weight of the compound.

In certain embodiments, R₃ is —CH₂—CH₂—, and R₃₁ is hydrogen. In theseembodiments, the —N(R₃₁)—R₃— repeat unit can be interrupted in one ormore places by a 1,4-diethylenediamine.

In accordance with another aspect of the subject matter disclosedherein, a method is provided for preparing a compound (or additive),such as the compound described above. The method includes:

(a) converting a polymer base unit R₁₁, which is a branched orstraight-chained C₁₀-C₈₀₀ alkyl or alkenyl group having a vinyl terminalgroup, to a polymer having polyanhydride terminal group represented by:

wherein y is an integer between 1 and 20 inclusive, a and b are C—Cbonds in cis-configuration with respect to each other and in either cis-or trans-configuration with respect to bond c; and

(b) reacting the polymer obtained in (a) with a polyamine represented by

wherein R₁₂ is hydrogen or a C₁-C₄ branched or straight chained alkyloptionally substituted with one or more amine groups, R₁₃ is a C₁-C₄branched or straight chained alkylene group, and x is an integer between1 and 10, and further wherein the —N(R₁₂)—R₁₃— unit is optionallyinterrupted in one or more places by a nitrogen-containing heterocycliccycloalkyl group, and wherein when the x-th —N(R₁₂)—R₁₃— unit along withthe terminal nitrogen atom forms a heterocyclic cycloalkyl group, theterminal —NH₂ is replaced by a —NH— group for valency.

In certain embodiments of the compound, y can be an integer between 1and 10 inclusive, or between 1 and 5 inclusive.

In certain embodiments of the above method, the polymer base unit R₁₁has a number-averaged molecular weight of 300 to 30,000 g/mol (assumingone olefin unsaturation per chain, as measured by ¹H NMR), andalternatively, about 500 to 5,000 g/mol.

In some embodiments of the above method, the polymer base unit R₁₁comprises polypropylene. The polypropylene can be either atacticpolypropylene or isotactic polypropylene. The polypropylene can beamorphous, and can include isotactic or syndiotactic crystallizableunits. In some embodiments, the polypropylene includes meso diadsconstituting from about 30% to about 99.5% of the total diads of thepolypropylene. The polymer base unit R₁₁ can also comprise polyethylene.

In alternative embodiments, the polymer base unit R₁₁ comprisespoly(ethylene-co-propylene). The poly(ethylene-co-propylene) can containfrom about 1 or 10 mole % to about 90 or 99 mole % of ethylene units andfrom about 99 or 90 mole % to about 10 or 1 mole % propylene units. Inone embodiment, the poly(ethylene-co-propylene) polymer contains fromabout 2 or 20 mole % to about 50 mole % ethylene units.

In one embodiment, the PP or EP included in the R₁₁ of the additiveFormula I, individually, have a number-averaged molecular weight (M_(n))from about 300 to about 30,000 g/mol, or from about 500 to about 5000g/mol (assuming one olefin unsaturation per chain, as measured by ¹HNMR). In one embodiment, the PP or EP groups have a molecular weight,individually, ranging from about 500 to about 2500 g/mol, or a molecularof from about 500 to about 650 g/mol, or a molecular weight of fromabout 800 to about 1000 g/mol, or a molecular weight of from about 2000to about 2500 g/mol.

In embodiments where the polymer base unit R₁₁ include polypropylene orpoly(ethylene-co-propylene), such groups can be prepared, for example,by metallocene-catalyzed polymerization of propylene or a mixture ofethylene and propylene, which are then terminated with a high vinylgroup content in the chain end. The number-averaged molecular weight(M_(n)) of the PP or EP can be from about 300 to about 30,000 g/mol, asdetermined by ¹H NMR spectroscopy. The vinyl-terminated atactic orisotactic polypropylenes (v-PP) or vinyl-terminatedpoly(ethylene-co-propylene) (v-EP) suitable for further chemicalfunctionalization can have a molecular weight (M_(n)) approximately fromabout 300 to about 30,000 g/mol, and preferably about 500 to 5,000g/mol. The terminal olefin group can be a vinylidene group or an allylicvinyl group (both covered in Formula I). In certain embodiments, theterminal olefin group is an allylic vinyl group. In this regard, theterminal allylic vinyl group rich PP or EP as disclosed in U.S. Pat. No.8,372,930 and co-pending application, U.S. Patent ApplicationPublication No. 20090318646, can be used, each of which is herebyincorporated by reference in its entirety. Some of the vinyl terminatedEP or PP according to these co-pending applications contains more than90% of allylic terminal vinyl group.

In some embodiments of the above method, R₁₁ can comprise propylene andless than 0.5 wt % comonomer, preferably 0 wt % comonomer, wherein theR₁₁ has:

i) at least 93% allyl chain ends (preferably at least 95%, preferably atleast 97%, preferably at least 98%);

ii) a number average molecular weight (Mn) of about 500 to about 20,000g/mol, as measured by ¹H NMR, assuming one olefin unsaturation per chain(preferably 500 to 15,000, preferably 700 to 10,000, preferably 800 to8,000 g/mol, preferably 900 to 7,000, preferably 1000 to 6,000,preferably 1000 to 5,000);

iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.3:1.0;

iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm,preferably less than 1000 ppm, preferably less than 500 ppm, preferablyless than 100 ppm).

In some embodiments of the above method, R₁₁ can comprise a propylenecopolymer having an Mn of 300 to 30,000 g/mol as measured by 1H NMR andassuming one olefin unsaturation per chain (preferably 400 to 20,000,preferably 500 to 15,000, preferably 600 to 12,000, preferably 800 to10,000, preferably 900 to 8,000, preferably 900 to 7,000 g/mol),comprising 10 to 90 mol % propylene (preferably 15 to 85 mol %,preferably 20 to 80 mol %, preferably 30 to 75 mol %, preferably 50 to90 mol %) and 10 to 90 mol % (preferably 85 to 15 mol %, preferably 20to 80 mol %, preferably 25 to 70 mol %, preferably 10 to 50 mol %) ofone or more alpha-olefin comonomers (preferably ethylene, butene,hexene, or octene, or decene, preferably ethylene), wherein the polymerhas at least X % allyl chain ends (relative to total unsaturations),where X is 80% or more, preferably 85% or more, preferably 90% or more,preferably 95% or more. Alternatively, R₁₁ can have at least 80%isobutyl chain ends (based upon the sum of isobutyl and n-propylsaturated chain ends), preferably at least 85% isobutyl chain ends,preferably at least 90% isobutyl chain ends. Alternately, R₁₁ can havean isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0,preferably 0.9:1 to 1.20:1.0, preferably 0.9:1.0 to 1.1:1.0.

In other embodiments, R₁₁ can comprise a polypropylene copolymer havingmore than 90 mol % propylene (preferably 95 to 99 mol %, preferably 98to 9 mol %) and less than 10 mol % ethylene (preferably 1 to 4 mol %,preferably 1 to 2 mol %), wherein the copolymer has:

at least 93% allyl chain ends (preferably at least 95%, preferably atleast 97%, preferably at least 98%);

a number average molecular weight (Mn) of about 400 to about 30,000g/mol, as measured by ¹H NMR and assuming one olefin unsaturation perchain (preferably 500 to 20,000, preferably 600 to 15,000, preferably700 to 10,000 g/mol, preferably 800 to 9,000, preferably 900 to 8,000,preferably 1000 to 6,000);

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0,and

less than 1400 ppm aluminum, (preferably less than 1200 ppm, preferablyless than 1000 ppm, preferably less than 500 ppm, preferably less than100 ppm).

In alternative embodiments, R₁₁ can comprise a polypropylene copolymercomprising:

at least 50 (preferably 60 to 90, preferably 70 to 90) mol % propyleneand from 10 to 50 (preferably 10 to 40, preferably 10 to 30) mol %ethylene, wherein the polymer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a Mn of about 150 to about 20,000 g/mol, as measured by ¹H NMR andassuming one olefin unsaturation per chain (preferably 200 to 15,000,preferably 250 to 15,000, preferably 300 to 10,000, preferably 400 to9,500, preferably 500 to 9,000, preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.3:1.0,wherein monomers having four or more carbon atoms are present at from 0to 3 mol % (preferably at less than 1 mol %, preferably less than 0.5mol %, preferably at 0 mol %).

In further embodiments, R₁₁ can comprise a polypropylene copolymercomprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % C₄ to C₁₂ olefin (such as butene,hexene or octene, or decene, preferably butene), wherein the polymerhas:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 15,000g/mol, as measured by ¹H NMR and assuming one olefin unsaturation perchain (preferably 200 to 12,000, preferably 250 to 10,000, preferably300 to 10,000, preferably 400 to 9500, preferably 500 to 9,000,preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0.

In certain embodiments, R₁₁ can comprise a polypropylene copolymercomprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % diene (such as C₄ to C₁₂ alpha-omegadienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidenenorbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene),wherein the polymer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 20,000g/mol, as measured by ¹H NMR and assuming one olefin unsaturation perchain (preferably 200 to 15,000, preferably 250 to 12,000, preferably300 to 10,000, preferably 400 to 9,500, preferably 500 to 9,000,preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0.

In other embodiments of the method, R₁₁ can comprises poly(higheralpha-olefin) or poly(propylene-co-higher alpha-olefin), the higheralpha-olefin including two or more carbon atoms on each side chain. Forexample, suitable higher alpha-olefins can include, but are not limitedto, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-hexadecene, 1-octadecene and the like.

In certain embodiments, R₁₁ includes those vinyl terminatedmacromonomers disclosed in U.S. Patent Application Publication Nos.20120245312, 20120245310, 20120245311, 20120245313, and U.S. ProvisionalApplication No. 61/704,604, the disclosure of each of which isincorporated by reference in its entirety herein.

In the above method of preparation, for the reaction of converting apolymer base unit R₁₁ having a terminal vinyl functionality, a reactionknown as ring opening cross metathesis (ROCM) reaction can be employed.As a general example, the ring opening cross metathesis of avinyl-terminated polypropylene (PP), ethylene-propylene (EP), orpropylene-higher alpha-olefin copolymer with a cyclic olefin,norbornene-exo-2,3-dicarboxylic anhydride, is illustrated in Scheme 1below.

Other examples of cyclic olefin include norbornene-endo-2,3-dicarboxylicanhydride.

In certain embodiments, the reactants for the ROCM reaction (includingthe R₁₁ and the cyclic olefin) can be combined in a reaction vessel at atemperature of 20° C. to 200° C. (e.g., 50° C. to 160° C., or 60° C. to140° C.) and a pressure of 0 MPa to 1000 MPa (e.g., 0.5 MPa to 500 MPa,or 1 MPa to 250 MPa) for a residence time of 0.5 seconds to 10 hours(e.g., 1 second to 5 hours, or 1 minute to 1 hour). The molecular weightof the polymer products can be controlled by, inter alia, choice ofcatalyst, ratio of R₁₁ to cyclic olefin, and/or possibly temperature.

As embodied herein, the ROCM reaction is performed in the presence of ametathesis catalyst. Catalysts suitable for the ROCM reaction caninclude those disclosed in U.S. Pat. Nos. 8,283,419 and 8,063,232; U.S.Patent Application Publication No. 20120309998, the disclosure of eachof which is incorporated by reference in its entirety herein. In certainembodiments, the catalyst is a tungsten or ruthenium metal complex-basedmetathesis catalyst. In certain embodiments, the catalyst is((t-Bu)₂PH)₂Cl₂Ru═CHCH═C(CH₃)₂, which can be prepared as described inU.S. Patent Application Publication No. 20120309998.

The quantity of metathesis catalyst employed in the ROCM can be aquantity that provides for an operable metathesis reaction. For example,the ratio of moles of reactants (including cyclic olefins and vinylterminated macromonomer) to moles of metathesis catalyst can be greaterthan 10:1, or greater than 100:1, or greater than 1,000:1, or greaterthan 10,000:1, or greater than 25,000:1, or greater than 50,000:1, orgreater than 100,000:1). In some examples, 0.00001 moles to 1.0 moles,or 0.0001 moles to 0.05 moles, or 0.0005 moles to 0.01 moles of catalystcan be charged to the reactor per mole of R₁₁ charged.

In some embodiments, the charge ratio of R₁₁ to cyclic olefin can be1:100 to 100:1, or 1:1 to 1:50 depending on the product sought. In somepreferred embodiments, the charge ratio of R11 to cyclic olefin is 1:1to 1:10. In more preferred embodiments, the ratio is 1:5, or morepreferably 1:3.

Other conditions and operating parameters of the ROCM reaction includethose disclosed in International Application PCT/US2012/059191, thedisclosure of which is incorporated by reference in its entirety herein.

As previously noted, the method of preparing the compound can includereacting the polymer obtained above with a polyamine (PAM). Thepolyamine can include linear, branched or cyclic isomers of an oligomerof ethyleneamine, or mixtures thereof, wherein each two neighboringnitrogens in the oligomer of ethyleneamine are bridged by one or twoethyleneamine groups. For example, the polyamine can be selected frompolyethyleneamines with general molecular formula H₂N(CH₂CH₂NH)_(x)H(where x=1, 2, 3, . . . ) such as ethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,hexaethyleneheptamine, and mixtures thereof. In some embodiments, thepolyamine can comprise a heavy polyamine, such as polyethyleneamineheavy bottoms available from Dow Chemical as “Heavy Polyamine X” orHPA-X.

For example and as embodied herein, the reaction can include reactingthe polymer having polyanhydride terminal group (as illustrated by theproduct obtained from Scheme 1) with a polyamine to provide the compoundas depicted in Scheme 2 below. In certain embodiments, the reaction isconducted at a temperature between ambient temperature and an elevatedtemperature from 100 to 180 C in an inert solvent for azeotropic removalof water generated by the reaction. Examples of suitable solvents forazeotrope formation with water include benzene, toluene and xylenes.Additional hydrocarbon solvents with a higher boiling point can also beused, preferably with water removal, such as by a vacuum, to drive thereaction to completion. In certain embodiments, the reaction is carriedout at ambient pressure. In other embodiments, the reaction is carriedout at elevated pressure to increase the rate of reaction, andsubsequently under low pressure to facilitate water removal. Reactiontimes can vary depending on reaction conditions. Generally, no specialcatalyst is required for the reaction.

The charge molar ratio of the polymer having the polyanhydride terminalgroup with the PAM can be from 20:1 to 1:20, and in some embodiments,5:1 to 1:1, depending on the product sought.

In the above illustrative example, a commercially available heavypolyamine (with about 6.5 nitrogen atoms per molecule on average) fromthe Dow Chemical Company (Heavy Polyamine X) is used as the polyamine.The number of polymer chain attached to each polyamine molecule can varyfrom one to two to three or more. In addition, both primary andsecondary amino groups on the polyamine can participate in the reactionwith the anhydride-functionalized polymer. Other commercially availablelower or higher polyamines with linear, branched, cyclic or heterocyclicstructures can also be used. It is well-known and understood by thoseskilled in the art that these polyamines can be mixtures of compoundscomprised of molecules with a distribution of chain lengths, differentlevel and type of amine (primary, secondary, and tertiary) functionalgroups, and varying degree of linear, branched and cyclic structures.For example, possible isomers for tetraethylenepentamine include thefollowing:

As the molecular weight of polyamines increases, the number of possibleisomers increases as well.

In another aspect of the disclosed subject matter, a compound (additive)is prepared by the method discussed above and various embodimentsthereof.

In another aspect, and as described further below with regard to anexemplary system, a method for reducing fouling in a hydrocarbonrefining process is provided, which comprises providing a crudehydrocarbon for a refining process, and adding to the crude hydrocarbonan additive of Formula I or various embodiments thereof as describedabove (e.g., at standard operation conditions).

Another aspect of the disclosed subject matter provides a system forrefining hydrocarbons that includes at least one crude hydrocarbonrefinery component, in which the crude hydrocarbon refinery componentincludes an additive selected from any one of the additives describedherein. The crude hydrocarbon refining component can be selected from aheat exchanger, a furnace, a crude preheater, a coker preheater, a FCCslurry bottom, a debutanizer exchanger, a debutanizer tower, afeed/effluent exchanger, a furnace air preheater, a flare compressorcomponent, a steam cracker, a steam reformer, a distillation column, afractionation column, a scrubber, a reactor, a liquid-jacketed tank, apipestill, a coker, and a visbreaker. For example, the crude hydrocarbonrefining component can be a heat exchanger (e.g., a crude pre-heat trainheat exchanger). Such methods and systems are described in greaterdetails in the following sections and examples.

Another aspect of the disclosed subject matter provides a compositionfor reducing fouling that includes at least one of any of theabove-described additives, and a boronating agent. The boronating agentcan be any one or more compounds selected from boric acid, anortho-borate, or a meta-borate, for example, boric acid, trimethylmetaborate (trimethoxyboroxine), triethyl metaborate, tributylmetaborate, trimethyl borate, triethylborate, triisopropyl borate(triisopropoxyborane), tributyl borate (tributoxyborane) and tri-t-butylborate. Other boronating agents can be used, such as those disclosed inco-pending applications US20100038290 and US20100170829, eachincorporated by reference herein in its entirety.

Further Compositions for Reducing Fouling

The additives of the disclosed subject matter can be used incompositions that prevent fouling, including particulate-inducedfouling. In addition to the additives of the disclosed subject matter,the compositions can further contain a hydrophobic oil solubilizer forthe additive and/or a dispersant for the additive.

Suitable solubilizers can include, for example, surfactants, carboxylicacid solubilizers, such as the nitrogen-containing phosphorous-freecarboxylic solubilizers disclosed in U.S. Pat. No. 4,368,133, herebyincorporated by reference in its entirety.

Also as disclosed in U.S. Pat. No. 4,368,133, hereby incorporated byreference in its entirety, surfactants that can be included incompositions of the disclosed subject matter can include, for example,cationic, anionic, nonionic or amphoteric type of surfactant. See, forexample, McCutcheon's “Detergents and Emulsifiers”, 1978, North AmericanEdition, published by McCutcheon's Division, MC Publishing Corporation,Glen Rock, N.J., U.S.A., including pages 17-33, which is herebyincorporated by reference in its entirety.

The compositions of the disclosed subject matter can further include,for example, viscosity index improvers, anti-foamants, antiwear agents,demulsifiers, anti-oxidants, and other corrosion inhibitors.

Furthermore, the additives of the disclosed subject matter can be addedwith other compatible components that address other problems that canpresent themselves in an oil refining process known to one of ordinaryskill in the art.

Uses of the Additives and Compositions in a Refinery Process

The additives of the disclosed subject matter are generally soluble in atypical hydrocarbon refinery stream and can thus be added directly tothe process stream, alone or in combination with other additives thateither reduce fouling or improve some other process parameter.

The additives can be introduced, for example, upstream from theparticular crude hydrocarbon refinery component(s) (e.g., a heatexchanger) in which it is desired to prevent fouling (e.g.particulate-induced fouling). Alternatively, the additive can be addedto the crude oil prior to being introduced to the refining process, orat the very beginning of the refining process.

In certain embodiments of the disclosed subject matter, the additive isdissolved in an inert carrier solvent to reduce the material viscosityof the additive. The additive can be dissolved in the carrier solvent bya mechanical blending process. Suitable carrier solvents include but arenot limited to naphtha, mineral oil, hydrocarbon fluid and paraffinicoil. For example, the additive is diluted with solvent until theviscosity of the resulting solution is acceptable for pumping andtransfer of the additive blend to the crude oil stream at ambientconditions. As embodied herein, the additive is diluted until theresulting solution is acceptable for pumping and transfer of theadditive blend to the crude oil stream at ambient conditions inrefineries subject to cold climates.

It is noted that water can have a negative impact on boron-containingadditives. Accordingly, it is advisable to add boron-containingadditives at process locations that have a minimal amount of water.

While not limited thereto, the additives of the disclosed subject matterare particularly suitable in reducing or preventing particulate-inducedfouling. Thus one aspect of the disclosed subject matter provides amethod of reducing and/or preventing, in particular, particulate-inducedfouling that includes adding at least one additive of the disclosedsubject matter to a process stream that is known, or believed tocontribute to, particulate-induced fouling. To facilitate determinationof proper injection points, measurements can be taken to ascertain theparticulate level in the process stream. Thus, one embodiment of thedisclosed subject matter includes identifying particular areas of arefining process that have relatively high particulate levels, andadding any one of the additives of the disclosed subject matter in closeproximity to these areas (e.g., just upstream to the area identified ashaving high particulate levels).

In some embodiments of the disclosed subject matter, a method to reducefouling is provided comprising adding any one of the above-mentionedadditives or compositions to a crude hydrocarbon refinery component thatis in fluid communication with a process stream that contains, at least50 wppm of particulates, including organic and inorganic particulates.In another embodiment of the disclosed subject matter, a method toreduce fouling is provided comprising adding any one of theabove-mentioned antifouling additives or compositions to a crudehydrocarbon refinery component that is in fluid communication with aprocess stream. In another embodiment of the disclosed subject matter, amethod to reduce fouling is provided comprising adding any one of theabove-mentioned additives to a crude hydrocarbon refinery component thatis in fluid communication with a process stream that contains at least250 wppm (or 1000 wppm, or 10,000 wppm) of particulates, includingorganic and inorganic particulates, as defined above.

In some embodiments of the disclosed subject matter, the additives orcompositions of the disclosed subject matter are added to selected crudeoil process streams known to contain, or possibly contain, problematicamounts of organic or inorganic particulate matter (e.g. 1-10,000 wppm),such as inorganic salts. Accordingly, the additives of the disclosedsubject matter can be introduced far upstream, where the stream isrelatively unrefined (e.g. the refinery crude pre-heat train). Theadditives can be also added, for example, after the desalter tocounteract the effects of incomplete salt removal or to the bottoms exitstream from the fractionation column to counteract the high temperaturesthat are conducive to fouling.

FIG. 1 demonstrates possible additive injection points within therefinery crude pre-heat train for the additives of the disclosed subjectmatter, wherein the numbered circles represent heat exchangers. As shownin FIG. 1, the additives can be introduced in crude storage tanks and atseveral locations in the preheat train. This includes at the crudecharge pump (at the very beginning of the crude pre-heat train), and/orbefore and after the desalter, and/or to the bottoms stream from a flashdrum.

The total amount of additive to be added to the process stream can bedetermined by a person of ordinary skill in the art. In one embodiment,up to about 1000 wppm of additive is added to the process stream. Forexample, the additive can be added such that its concentration, uponaddition, is about 50 ppm, 250 ppm or 500 ppm. More or less additive canbe added depending on, for example, the amount of particulate in thestream, the ΔT associated with the particular process and the degree offouling reduction desired in view of the cost of the additive.

The additives or compositions of the disclosed subject matter can beadded in a solid (e.g. powder or granules) or liquid form directly tothe process stream. As mentioned above, the additives or compositionscan be added alone, or combined with other components to form acomposition for reducing fouling (e.g. particulate-induced fouling). Anysuitable technique can be used for adding the additive to the processstream, as known by a person of ordinary skill in the art in view of theprocess to which it is employed. As a non-limiting example, theadditives or compositions can be introduced via injection that allowsfor sufficient mixing of the additive and the process stream.

EXAMPLES

The disclosed subject matter is further described by means of theexamples, presented below. The use of such examples is illustrative onlyand in no way limits the scope and meaning of the disclosed subjectmatter or of any exemplified term. Likewise, the disclosed subjectmatter is not limited to any particular preferred embodiments describedherein. Indeed, many modifications and variations of the disclosedembodiments will be apparent to those skilled in the art upon readingthis specification.

Example 1 Synthesis of Compounds

A. Ring Opening Cross Metathesis Reaction ofnorbornene-exo-2,3-dicarboxylic Anhydride with Vinyl Terminatedpropylene/1-butene Copolymer

The general scheme of the synthesis is shown in Scheme 3 below.

An oven dried 250 mL round bottom flask was charged in the drybox withthe vinyl terminated propylene/1-butene copolymer (47.0 g, ˜27.2 mmol),norbornene-exo-2,3-dicarboxylic anhydride (7.7 g, 46.9 mmol) and CHCl₃(50 mL). The solution was heated to 50° C. and stirred for two hours tohomogenize the poorly soluble anhydride. The solution was analyzed by¹H-NMR showing a molar ratio of approximately 2 norbornene anhydride toone vinyl terminated butene-propylene copolymer vinyl group. Thecatalyst, ((t-Bu)₂PH)₂Cl₂Ru═CHCH═C(CH₃)₂, was added in one portion andstirred at 50° C. for 2 hours. The reaction was quenched using 1 g ofsilica, and the CHCl₃ was removed under vacuum at 45° C. overnight. Thetranslucent brown polymer was treated with approximately 150 mL ofpentane. The mixture was heated to 40° C. and stirred for several hoursto homogenize the mixture. The mixture was then cooled for 2 hours to−25° C. This mixture was then filtered using a plug of silica, followedby further filtration through 1 micron syringe filters. The solvent wasremoved under a stream of nitrogen gas. The polymer product was dried bysparging nitrogen gas directly into the polymer while heating it to 80°C. The dried polymer product was obtained as a colorless viscous product(37.9 g) and analyzed by 1H-NMR: 400 MHz (C₂D₂Cl₄): δ 5.9 (m, 0.32H),5.3-5.7 (m, 1.35H), 5.1-5.3 (m, 0.57H), 2.75-3.5 (m, 2.51H), 0.5-2.5 (m,93.9H). ¹H-NMR showed 100% conversion of the vinyl terminatedpropylene/1-butene copolymer starting material. The degree of ROCM, ornumber of norbornene anhydride units on the end of the functionalizedpolymer, was determined to be 2.4 by Method A and was calculated to be2.2 by Method B below.

Method A

The degree of ROCM was calculated by the ratio of the ¹H-NMR integrationof total internal olefin (5.3 ppm-5.7 ppm) to the CH₂ olefin in thefunctionalized polymer (5.1 ppm-5.3 ppm):

${{Degree}\mspace{14mu}{of}\mspace{14mu}{ROCM}\mspace{14mu}\left( {{method}\mspace{14mu} A} \right)} = {\frac{\int{{int}\mspace{14mu}{olefin}}}{\int{= {{CH}_{2}({product})}}}.}$

Method B

Alternatively, the degree of ROCM can be calculated by the ratio of the¹H-NMR integration of product ring methine protons (2.75 ppm-3.5 ppm) tothe CH₂ olefin in the functionalized polymer (5.1 ppm-5.3 ppm).

${{Degree}\mspace{14mu}{of}\mspace{14mu}{ROCM}\mspace{14mu}\left( {{method}\mspace{14mu} B} \right)} = {\frac{\int{methine}}{\int{= {{CH}_{2}({product})}}}*{\frac{1}{2}.}}$

The above results indicate that little or no dimerization occurred.Catalyst turn over frequency (TON) was calculated to be 1,820. Molecularweight of the anhydride-functionalized polymer product as measured byGPC was 6855 (M_(w)) and 2888 (M_(n)). Elemental analyses for thepolymer product found C: 83.16%, H: 13.40%. The oxygen content of thecompound is estimated to be about 3.44 wt %. The anhydride content ofthis material is estimated to be about 0.717 mmol/g.

B. Functionalization of Anhydride-Functionalized propylene/1-buteneCopolymer with Heavy Polyamine X (HPA-X)

A solution of Heavy Polyamine X (0.985 g, 3.58) in xylenes (10 ml) wasadded to a solution of anhydride-functionalized propylene/1-butenecopolymer (10.00 g, from Example 1A) in xylenes (65 ml) in a two-neckround-bottomed flask over 5 minutes at room temperature. The resultingmixture was heated in an oil bath at 160° C. for 24 hours under anitrogen atmosphere. During the reaction an azeotropic mixture ofxylenes and water was collected in a Dean-Stark trap. The light brownmixture was cooled to room temperature and excess xylenes was removed ona rotary evaporator. The residual product was further purified byheating at 95° C. under high vacuum to afford a light brown viscousproduct (10.82 g). Elemental analyses for this propylene/1-butenecopolymer-polyamine additive found C: 81.34%, H: 13.07%, N: 3.15%.

Example 2 Fouling Reduction Measured in the Alcor HLPS (Hot LiquidProcess Simulator)

FIG. 2 depicts an Alcor HLPS (Hot Liquid Process Simulator) testingapparatus used to measure the impact of addition of particulates to acrude oil on fouling and the impact the addition of an additive of thedisclosed subject matter has on the mitigation of fouling. The testingarrangement includes a reservoir 10 containing a feed supply of crudeoil. The feed supply of crude oil can contain a base crude oilcontaining a whole crude or a blended crude containing two or more crudeoils. The feed supply is heated to a temperature of approximately 150°C./302° F. and then fed into a shell 11 containing a vertically orientedheated rod 12. The heated rod 12 is formed from carbon-steel (1018). Theheated rod 12 simulates a tube in a heat exchanger. The heated rod 12 iselectrically heated to a surface temperature of 370° C./698° F. or 400°C./752° F. and maintained at such temperature during the trial. The feedsupply is pumped across the heated rod 12 at a flow rate ofapproximately 3.0 mL/minute. The spent feed supply is collected in thetop section of the reservoir 10. The spent feed supply is separated fromthe untreated feed supply oil by a sealed piston, thereby allowing foronce-through operation. The system is pressurized with nitrogen (400-500psig) to ensure gases remain dissolved in the oil during the test.Thermocouple readings are recorded for the bulk fluid inlet and outlettemperatures and for surface of the rod 12.

During the constant surface temperature testing, foulant deposits andbuilds up on the heated surface. The foulant deposits are thermallydegraded to coke. The coke deposits cause an insulating effect thatreduces the efficiency and/or ability of the surface to heat the oilpassing over it. The resulting reduction in outlet bulk fluidtemperature continues over time as fouling continues. This reduction intemperature is referred to as the outlet liquid ΔT or ΔT and can bedependent on the type of crude oil/blend, testing conditions and/orother effects, such as the presence of salts, sediment or other foulingpromoting materials. A standard Alcor fouling test is carried out for180 minutes. The total fouling, as measured by the total reduction inoutlet liquid temperature over time, is plotted on the y-axis of FIG. 3and is the observed outlet temperature (T_(outlet)) minus the maximumobserved outlet T_(outlet max) (presumably achieved in the absence ofany fouling).

FIG. 3 illustrates the impact of fouling of a refinery component over180 minutes. Two blends were tested in the Alcor unit: a crude oilcontrol containing added rust (iron oxide) particles (200 wppm) withoutan additive, and the same stream with 25 wppm of the additive preparedaccording to the method in Example 1.B. above. As FIG. 3 demonstrates,the reduction in the outlet temperature over time (due to fouling) isless for the process blend containing 25 wppm of additive as compared tothe crude oil control without the additive. This indicates that theadditive is effective at reducing fouling of a heat exchanger.

Additional Embodiments

Additionally or alternately, the disclosed subject matter can includeone or more of the following embodiments.

The Embodiment 1

A compound represented by:

wherein R₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup; y is an integer between 1 to 20 inclusive; m is an integerbetween 0 and 10 inclusive; a and b are C—C bonds in cis-configurationwith respect to each other and in either cis- or trans-configurationwith respect to bond c; R₂ and R₃ are each independently a C₁-C₄branched or straight chained alkylene group; R₃₁ is hydrogen or —R₈-R₉,wherein either (a) R₈ is C₁-C₄ branched or straight chained alkylenegroup, and R₉ is

wherein R₉₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup, the asterisk (*) indicates a connecting point with R₈, d and eare C—C bonds in cis-configuration with respect to each other and ineither cis- or trans-configuration with respect to bond f, and z is aninteger between 1 to 20 inclusive; or (b) R₈ and R₉ together are a C₁-C₄branched or straight chained alkyl group optionally substituted with oneor more amine groups; and wherein the —N(R₃₁)—R₃— repeat unit isoptionally interrupted in one or more places by a nitrogen-containingheterocyclic cycloalkyl group; and

wherein R₄ and R₅ are each independently selected from (a) hydrogen, (b)—R₆-R₇, wherein R₆ is C₁-C₄ branched or straight chained alkylene group,and R₇ is

wherein R₇₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup, the asterisk (*) indicates a connecting point with R₆, g and hare C—C bonds in cis-configuration with respect to each other and ineither cis- or trans-configuration with respect to bond j, and q is aninteger between 1 to 20 inclusive; or (c) a bond connected to R₃₁ in them-th —N(R₃₁)—R₃— repeat unit.

Embodiment 2

The compound of Embodiment 1, wherein at least one of R₁, R₇₁, and R₉₁comprises polypropylene.

Embodiment 3

The compound of Embodiment 2, wherein the polypropylene is atacticpolypropylene, isotactic polypropylene, or syndiotactic polypropylene.

Embodiment 4

The compound of Embodiment 2, wherein the polypropylene is amorphous.

Embodiment 5

The compound of Embodiment 2, wherein the polypropylene includesisotactic or syndiotactic crystallizable units.

Embodiment 6

The compound of Embodiment 2, wherein the polypropylene includes mesodiads constituting from about 30% to about 99.5% of the total diads ofthe polypropylene.

Embodiment 7

The compound of Embodiment 2, wherein at least one of R₁, R₇₁, and R₉₁has a number-averaged molecular weight of from about 300 to about 30000g/mol.

Embodiment 8

The compound of Embodiment 7, wherein at least one of R₁, R₇₁, and R₉₁has a number-averaged molecular weight of from about 500 to about 5000g/mol.

Embodiment 9

The compound of Embodiment 1, wherein at least one of R₁, R₇₁, and R₉₁comprises polyethylene.

Embodiment 10

The compound of Embodiment 1, wherein at least one of R₁, R₇₁, and R₉₁comprises poly(ethylene-co-propylene).

Embodiment 11

The compound of Embodiment 10, wherein at least one of R₁, R₇₁, and R₉₁comprises from about 1 mole % to about 90 mole % of ethylene units andfrom about 99 mole % to about 10 mole % propylene units.

Embodiment 12

The compound of Embodiment 11, wherein at least one of R₁, R₇₁, and R₉₁comprises from about 10 mole % to about 50 mole % of ethylene units.

Embodiment 13

The compound of Embodiment 1, wherein at least one of R₁, R₇₁, and R₉₁comprises poly(higher alpha-olefin), the higher alpha-olefin includingtwo or more carbon atoms on each side chain.

Embodiment 14

The compound of Embodiment 1, wherein at least one of R₁, R₇₁, and R₉₁comprises poly(propylene-co-higher alpha-olefin), the higheralpha-olefin including two or more carbon atoms on each side chain.

Embodiment 15

The compound according to any one of the previous Embodiments, whereinthe nitrogen content in the compound is about 1 wt % to about 10 wt %based on the total weight of the compound.

Embodiment 16

The compound according to any one of the previous Embodiments, whereinR₃ is —CH₂—CH₂—, and R₃₁ is hydrogen.

Embodiment 17

The compound of Embodiment 16, wherein the —N(R₃₁)—R₃— repeat unit isinterrupted in one or more places by a 1,4-diethylenediamine.

Embodiment 18

A method for preparing a compound, comprising: (a) converting a polymerbase unit R₁₁, which is a branched or straight-chained C₁₀-C₈₀₀ alkyl oralkenyl group having a vinyl terminal group, to a polymer havingpolyanhydride terminal group represented by:

wherein y is an integer between 1 and 20 inclusive, a and b are C—Cbonds in cis-configuration with respect to each other and in either cis-or trans-configuration with respect to bond c; and (b) reacting thepolymer obtained in (a) with a polyamine represented by

wherein R₁₂ is hydrogen or a C₁-C₄ branched or straight chained alkyloptionally substituted with one or more amine groups, R₁₃ is a C₁-C₄branched or straight chained alkylene group, and x is an integer between1 and 10, and further wherein the —N(R₁₂)—R₁₃— unit is optionallyinterrupted in one or more places by a nitrogen-containing heterocycliccycloalkyl group, and wherein when the x-th —N(R₁₂)—R₁₃— unit along withthe terminal nitrogen atom forms a heterocyclic cycloalkyl group, theterminal —NH₂ is replaced by a —NH— group for valency.

Embodiment 19

The method of Embodiment 18, wherein R₁₁ comprises polypropylene.

Embodiment 20

The method of Embodiment 19, wherein the polypropylene is atacticpolypropylene, isotactic polypropylene, or syndiotactic polypropylene.

Embodiment 21

The method of Embodiment 19, wherein the polypropylene is amorphous.

Embodiment 22

The method of Embodiment 19, wherein the polypropylene includesisotactic or syndiotactic crystallizable units.

Embodiment 23

The method of Embodiment 19, wherein the polypropylene includes mesodiads constituting from about 30% to about 99.5% of the total diads ofthe polypropylene.

Embodiment 24

The method of Embodiment 18, wherein the molar ratio of R_(H):polyamineis between about 5:1 and about 1:5.

Embodiment 25

The method of Embodiment 18, wherein R₁₁ has a number-averaged molecularweight of from about 300 to about 30000 g/mol.

Embodiment 26

The method of Embodiment 25, wherein R₁₁ has a number-averaged molecularweight of from about 500 to about 5000 g/mol.

Embodiment 27

The method of Embodiment 18, wherein R₁₁ comprises polyethylene.

Embodiment 28

The method of Embodiment 18, wherein R₁₁ comprisespoly(ethylene-co-propylene).

Embodiment 29

The method of Embodiment 18, wherein R₁₁ comprises from about 10 mole %to about 90 mole % of ethylene units and from about 90 mole % to about10 mole % propylene units.

Embodiment 30

The method of Embodiment 29, wherein R₁₁ comprises from about 20 mole %to about 50 mole % of ethylene units.

Embodiment 31

The method of Embodiment 18, wherein R₁₁ comprises poly(higheralpha-olefin), the higher alpha-olefin including two or more carbonatoms on each side chain.

Embodiment 32

The method of Embodiment 18, wherein R₁₁ comprisespoly(propylene-co-higher alpha-olefin), the higher alpha-olefinincluding two or more carbon atoms on each side chain.

Embodiment 33

The method of Embodiment 18, wherein R₁₁ comprisespoly(ethylene-co-higher alpha-olefin), the higher alpha-olefin includingtwo or more carbon atoms on each side chain.

Embodiment 34

The method of Embodiment 18, wherein at least 50% of the terminal vinylgroups of R₁₁ are an allylic vinyl group.

Embodiment 35

The method of Embodiment 18, wherein the polyamine comprises linear,branched or cyclic isomers of an oligomer of ethyleneamine, or mixturesthereof, wherein each two neighboring nitrogens in the oligomer ofethyleneamine are bridged by one or two ethyleneamine groups.

Embodiment 36

The method of Embodiment 35, wherein the polyamine is selected fromethylenediamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine,and mixtures thereof.

Embodiment 37

The method of Embodiment 18, wherein the polyamine comprises a heavypolyamine.

Embodiment 38

The method of Embodiment 18, wherein (a) comprises reacting the polymerhaving the terminal vinyl group with norbornene-exo-2,3-dicarboxylicanhydride.

Embodiment 39

The method of Embodiment 18, wherein (a) comprises reacting the polymerhaving the terminal vinyl group with norbornene-endo-2,3-dicarboxylicanhydride.

Embodiment 40

The method of Embodiment 18, wherein the reaction in (a) is a ringopening cross metathesis reaction catalyzed by a tungsten or rutheniummetal complex-based metathesis catalyst.

Embodiment 41

A compound produced by the method of any of Embodiments 18-40.

Embodiment 42

A method for reducing fouling in a hydrocarbon refining processcomprising providing a crude hydrocarbon for a refining process; addingan additive to the crude hydrocarbon, the additive being represented bythe compound of any of Embodiments 1-17.

Embodiment 43

A method for reducing fouling in a hydrocarbon refining processcomprising providing a crude hydrocarbon for a refining process; andadding an additive to the crude hydrocarbon, the additive being preparedby the method of any of Embodiments 18-40.

Embodiment 44

A system for refining hydrocarbons comprising: at least one crudehydrocarbon refinery component; and crude hydrocarbon in fluidcommunication with the at least one crude hydrocarbon refinerycomponent, the crude hydrocarbon comprising an additive represented bythe compound of any of Embodiments 1-17.

Embodiment 45

The system of Embodiment 44, wherein the at least one crude hydrocarbonrefinery component is selected from a heat exchanger, a furnace, a crudepreheater, a coker preheater, a FCC slurry bottom, a debutanizerexchanger, a debutanizer tower, a feed/effluent exchanger, a furnace airpreheater, a flare compressor component, a steam cracker, a steamreformer, a distillation column, a fractionation column, a scrubber, areactor, a liquid-jacketed tank, a pipestill, a coker, and a visbreaker.

The disclosed subject matter is not to be limited in scope by thespecific embodiments described herein. Indeed, various modifications ofthe invention in addition to those described herein will become apparentto those skilled in the art from the foregoing description and theaccompanying figures. Such modifications are intended to fall within thescope of the appended claims.

It is further to be understood that all values are approximate, and areprovided for description.

Patents, patent applications, publications, product descriptions, andprotocols are cited throughout this application, the disclosures of eachof which is incorporated herein by reference in its entirety for allpurposes.

What is claimed:
 1. A method for preparing a compound, comprising: (a)converting a polymer base unit R₁₁, which is a branched orstraight-chained C₁₀-C₈₀₀ alkyl or alkenyl group having a vinyl terminalgroup, to a polymer having polyanhydride terminal group represented by:

wherein y is an integer between 1 and 20 inclusive, a and b are C—Cbonds in cis-configuration with respect to each other and in either cis-or trans-configuration with respect to bond c; and (b) reacting thepolymer obtained in (a) with a polyamine represented by

wherein R₁₂ is hydrogen or a C₁-C₄ branched or straight chained alkyloptionally substituted with one or more amine groups, R₁₃ is a C₁-C₄branched or straight chained alkylene group, and x is an integer between1 and 10, and further wherein the —N(R₁₂)—R₁₃— unit is optionallyinterrupted in one or more places by a nitrogen-containing heterocycliccycloalkyl group, and wherein when the x-th —N(R₁₂)—R₁₃— unit along withthe terminal nitrogen atom forms a heterocyclic cycloalkyl group, theterminal —NH₂ is replaced by a —NH— group for valency.
 2. The method ofclaim 1, wherein R₁₁ comprises polypropylene.
 3. The method of claim 2,wherein the polypropylene is atactic polypropylene, isotacticpolypropylene, or syndiotactic polypropylene.
 4. The method of claim 2,wherein the polypropylene is amorphous.
 5. The method of claim 2,wherein the polypropylene includes isotactic or syndiotacticcrystallizable units.
 6. The method of claim 2, wherein thepolypropylene includes meso diads constituting from about 30% to about99.5% of the total diads of the polypropylene.
 7. The method of claim 1,wherein the molar ratio of R₁₁: polyamine is between about 5:1 and about1:5.
 8. The method of claim 1, wherein R₁₁ has a number-averagedmolecular weight of from about 300 to about 30000 g/mol.
 9. The methodof claim 8, wherein R₁₁ has a number-averaged molecular weight of fromabout 500 to about 5000 g/mol.
 10. The method of claim 1, wherein R₁₁comprises polyethylene.
 11. The method of claim 1, wherein R₁₁ comprisespoly(ethylene-co-propylene).
 12. The method of claim 1, wherein R₁₁comprises from about 10 mole % to about 90 mole % of ethylene units andfrom about 90 mole % to about 10 mole % propylene units.
 13. The methodof claim 12, wherein R₁₁ comprises from about 20 mole % to about 50 mole% of ethylene units.
 14. The method of claim 1, wherein R₁₁ comprisespoly(higher alpha-olefin), the higher alpha-olefin including two or morecarbon atoms on each side chain.
 15. The method of claim 1, wherein R₁₁comprises poly(propylene-co-higher alpha-olefin), the higheralpha-olefin including two or more carbon atoms on each side chain. 16.The method of claim 1, wherein R₁₁ comprises poly(ethylene-co-higheralpha-olefin), the higher alpha-olefin including two or more carbonatoms on each side chain.
 17. The method of claim 1, wherein at least50% of the terminal vinyl groups of R₁₁ are an allylic vinyl group. 18.The method of claim 1, wherein the polyamine comprises linear, branchedor cyclic isomers of an oligomer of ethyleneamine, or mixtures thereof,wherein each two neighboring nitrogens in the oligomer of ethyleneamineare bridged by one or two ethyleneamine groups.
 19. The method of claim18, wherein the polyamine is selected from ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, hexaethyleneheptamine, and mixtures thereof. 20.The method of claim 1, wherein the polyamine comprises a heavypolyamine.
 21. The method of claim 1, wherein (a) comprises reacting thepolymer having the terminal vinyl group withnorbornene-exo-2,3-dicarboxylic anhydride in the presence of ametathesis catalyst.
 22. The method of claim 1, wherein (a) comprisesreacting the polymer having the terminal vinyl group withnorbornene-endo-2,3-dicarboxylic anhydride.
 23. The method of claim 1,wherein the reaction in (a) is a ring opening cross metathesis reactioncatalyzed by a tungsten or ruthenium metal complex-based metathesiscatalyst.